JPH04266802A - Synergetically bactericidal composition of 2-(decylthio)ethaneamine and 1,2-dibromo- 2,4-dicyanobuthane - Google Patents

Synergetically bactericidal composition of 2-(decylthio)ethaneamine and 1,2-dibromo- 2,4-dicyanobuthane

Info

Publication number
JPH04266802A
JPH04266802A JP3307165A JP30716591A JPH04266802A JP H04266802 A JPH04266802 A JP H04266802A JP 3307165 A JP3307165 A JP 3307165A JP 30716591 A JP30716591 A JP 30716591A JP H04266802 A JPH04266802 A JP H04266802A
Authority
JP
Japan
Prior art keywords
decylthio
dibromo
dicyanobutane
microorganisms
ethanamine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP3307165A
Other languages
Japanese (ja)
Inventor
John C Tully
ジヨン・シー・タリー
Linda Young-Bandala
リンダ・ヤング−バンダラ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
WR Grace and Co
Original Assignee
WR Grace and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by WR Grace and Co filed Critical WR Grace and Co
Publication of JPH04266802A publication Critical patent/JPH04266802A/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/50Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34Nitriles

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Environmental Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

PURPOSE: To obtain a combination of two types of biocidal materials that give rise to synergistic effects against microorganisms in aqueous systems such that the extent to which the microorganisms are killed exceeds that which one would expect from using the sum of the individual components of the composition. CONSTITUTION: This combination comprises 2-(decylthio)ethaneamine and 1,2- dibromo-2,4-dicyanobutane in amounts effective to inhibit microbial growth. The combination has proven to be particularly effective in inhibiting the growth of Enterobacter aerogenes ATCC 13048 in aqueous systems.

Description

【発明の詳細な説明】[Detailed description of the invention]

【0001】0001

【産業上の利用分野】本発明は水系の処理に関し、及び
更に詳細には冷却水系、空気洗浄水系及び紙パルプ製造
装置のような工業的な水系中に一般に見出される微生物
に対して相乗作用的である殺菌性の物質に関する。
TECHNICAL FIELD This invention relates to the treatment of water systems, and more particularly to the treatment of microorganisms commonly found in industrial water systems such as cooling water systems, air washing water systems, and pulp and paper manufacturing equipment. Concerning a bactericidal substance.

【0002】0002

【従来の技術】微生物によるスライムの生成は多くの工
業的水系において遭遇する問題である。例えば工業的冷
却水系において、使用される水は一般に水道水であり、
大規模な設備の場合はしばしば未処理の河川水である。 このため水は滅菌されておらず、細菌が設備中に集積す
る結果をもたらす。更に設備水がタワーの送風機に沿っ
て落下する際に細菌の大きな部分が空気中に取り込まれ
る。このために冷却水と直接接触する設備の表面にスラ
イム状の沈着物が発生することが普通である。一回式(
once−through)及び再循環式冷却設備の両
者とも冷却媒体として大量の水を使用し、微生物による
スライムの生成は広範囲且つ恒常的な問題である。
BACKGROUND OF THE INVENTION Slime production by microorganisms is a problem encountered in many industrial water systems. For example, in industrial cooling water systems, the water used is generally tap water;
For large-scale installations, it is often untreated river water. As a result, the water is not sterile, resulting in bacteria building up in the equipment. Furthermore, as the facility water falls along the tower blowers, a large portion of the bacteria is introduced into the air. As a result, it is common for slime-like deposits to form on the surfaces of equipment that come into direct contact with the cooling water. One-time formula (
Both once-through and recirculating refrigeration equipment use large amounts of water as the cooling medium, and slime formation by microorganisms is a widespread and constant problem.

【0003】スライムの生成は木製のタワーの場合タワ
ー構造の劣化を招くのみならず、設備を詰まらせ、及び
放置したまま集積されれば設備を非効率なものとする傾
向がある。冷却設備を通って運搬されるスライムは配管
、バルブ、ストレーナー等を詰まらせ及び汚す。水中に
あって水系を通って運搬される細菌は熱交換機の表面の
ような表面部位に集積し、熱交換を妨げ、冷却設備の効
率を大きく減少させるスライムの塊を形成する。スライ
ムの集積は又スライムの下の低酸素環境中で繁殖する嫌
気性細菌の成長を招く環境を提供する。これらの嫌気性
微生物は金属表面の点蝕及び腐蝕を起こす可能性がある
[0003] Slime formation not only causes deterioration of the tower structure in the case of wooden towers, but also tends to clog the equipment and render the equipment inefficient if left to accumulate. Slime transported through the cooling equipment clogs and fouls piping, valves, strainers, etc. Bacteria that are in the water and transported through the water system accumulate on surface sites, such as the surfaces of heat exchangers, forming slime clumps that impede heat exchange and greatly reduce the efficiency of cooling equipment. Slime accumulation also provides an environment conducive to the growth of anaerobic bacteria that thrive in the low oxygen environment beneath the slime. These anaerobic microorganisms can cause pitting and corrosion of metal surfaces.

【0004】紙パルプ製造装置においては、微生物によ
り形成されたスライムは普通に遭遇されるものであり、
設備の汚染、目詰まり、又は腐蝕を起こす。スライムは
又製造された紙中に取り込まれて抄紙機上にブレークア
ウトを起こし、作業の停止及び生産時間の損失をもたら
す。スライムは又最終生成物の見苦しい汚れの原因とな
り、拒絶及び生産物の廃棄を招く。
Slime formed by microorganisms is commonly encountered in paper pulp manufacturing equipment.
Causing equipment contamination, clogging, or corrosion. Slime can also be incorporated into the manufactured paper and cause breakouts on the paper machine, resulting in work stoppages and loss of production time. Slime also causes unsightly staining of the final product, leading to rejection and product waste.

【0005】[0005]

【発明が解決しようとする課題】以上論じた問題は冷却
水中及び紙パルプ製造設備中での殺菌剤の広範囲な利用
をもたらした。塩素、塩素化フェノール、有機臭素、及
び各種の有機硫黄化合物を含む各種の物質がこうした用
途に使用された。これらの化合物の総ては一般にこの目
的に有用であるが、各々は各種の障害を伴っている。例
えば塩素化は経済的濃度におけるスライム形成微生物に
対する特異的毒性、及び充分な殺菌的機能が達成される
前に塩素の消費を招く塩素の反応傾向の両者により制限
されている。他の殺菌剤はそれらの利用を制限する臭気
の問題及び貯蔵、使用又は取り扱いに関する危険を伴っ
ている。今日まで上に論じたような用途に関して明らか
に確立された優越性を達成した化合物又は化合物の種類
は一つもない。
The problems discussed above have led to the widespread use of disinfectants in cooling water and pulp and paper manufacturing equipment. A variety of materials have been used in these applications, including chlorine, chlorinated phenols, organobromine, and various organosulfur compounds. Although all of these compounds are generally useful for this purpose, each is associated with various drawbacks. For example, chlorination is limited both by its specific toxicity to slime-forming microorganisms at economical concentrations and by the reactive tendency of chlorine to result in consumption of the chlorine before full biocidal function is achieved. Other disinfectants are associated with odor problems and storage, use, or handling hazards that limit their use. To date, no single compound or class of compounds has achieved clearly established superiority for the applications discussed above.

【0006】殺菌剤の使用は処理される設備への連続的
又は頻繁な添加を含み、及びこれらの設備内の多数の点
又は帯域への添加を必要とする。
The use of disinfectants involves continuous or frequent addition to the equipment being treated and requires addition to multiple points or zones within these equipment.

【0007】[0007]

【課題を解決するための手段】水系中における微生物の
成長を防止する新規殺菌性組成物を提供することが本発
明の目的である。
SUMMARY OF THE INVENTION It is an object of the present invention to provide novel fungicidal compositions that prevent the growth of microorganisms in aqueous systems.

【0008】水系中の微生物に対して相乗作用のある2
−(デシルチオ)エタンアミン及び1,2−ジブロモ−
2,4−ジシアノブタンの組み合わせを含む殺菌性組成
物を提供することが本発明の他の目的である。
2 which has a synergistic effect on microorganisms in water systems
-(decylthio)ethanamine and 1,2-dibromo-
It is another object of the present invention to provide a fungicidal composition comprising a combination of 2,4-dicyanobutane.

【0009】本発明によれば、1,2−ジブロモ−2,
4−ジシアノブタン及び2−(デシルチオ)エタンアミ
ンの混合物を含む殺菌性組成物、及び微生物の成長を阻
害するのに効果的な量で水系に組成物を添加する該組成
物の使用方法が提供される。
According to the invention, 1,2-dibromo-2,
A fungicidal composition comprising a mixture of 4-dicyanobutane and 2-(decylthio)ethanamine and a method of using the composition is provided, the composition being added to an aqueous system in an amount effective to inhibit the growth of microorganisms. Ru.

【0010】本発明は微生物を殺菌する範囲が、組成物
の個々の成分の合計量を使用することから予想される範
囲を超えるような相乗的な効果を水系中の微生物に対し
て及ぼす、二種類の殺菌性物質の併用を志向している。 更に詳細には、本発明は微生物の成長を防止するのに有
効な量で2−(デシルチオ)エタンアミン及び1,2−
ジブロモ−2,4−ジシアノブタンを含んで成る組み合
わせを志向している。この組み合わせは水系中でエンテ
ロバクター・アエロゲネス(Enterobacter
 aero−genes)ATCC13048の成長を
阻害するのに特に有効であることが認められている。
[0010] The present invention provides two methods that have a synergistic effect on microorganisms in an aqueous system such that the extent of microbial killing exceeds that expected from the use of the total amounts of the individual components of the composition. It is intended to be used in combination with various bactericidal substances. More particularly, the invention provides 2-(decylthio)ethanamine and 1,2-ethanamine in an amount effective to prevent microbial growth.
A combination comprising dibromo-2,4-dicyanobutane is desired. This combination is effective against Enterobacter aerogenes (Enterobacter aerogenes) in water systems.
aero-genes) ATCC 13048.

【0011】2−(デシルチオ)エタンアミンは米国特
許第4,816,061号によりDTEA又はXU40
304.01Lの名称でダウ・ケミカル(Dow Ch
emical)社により製造されている。1,2−ジブ
ロモ−2,4−ジシアノブタンは米国特許第3,833
,731号、3,873,597号、3,877,92
2号及び3,929,858号に従ってカルゴン(Ca
lgon)社のメルク・ケミカル(Merck Che
mical)部門により製造されている。
2-(decylthio)ethanamine is synthesized by DTEA or XU40 according to US Pat. No. 4,816,061.
Dow Chemical (Dow Ch.
Manufactured by the company ``Emical''. 1,2-dibromo-2,4-dicyanobutane is disclosed in U.S. Patent No. 3,833.
, No. 731, No. 3,873,597, No. 3,877,92
2 and 3,929,858.
Merck Chemical (Merck Chem.
mical) division.

【0012】本発明の殺菌性組成物は一般に7より高い
pH、好適には8ないし9のpHを有する水系に添加さ
れる時に最も効果的である。本発明の組成物の個々の殺
菌成分は別個に又は予備混合して水系に添加することが
でき、微生物の成長を阻害するのに効果的な量で添加さ
れる。2−(デシルチオ)エタンアミンは一般に0.7
ないし1.2ppmの濃度で水系に添加され、1,2−
ジブロモ−2,4−ジシアノブタンは一般に4.0ない
し12.0ppmの濃度範囲で添加される。水系中の殺
菌剤の合計濃度は一般に5ないし14ppm、及び好適
には5.2ないし13.2ppmの範囲である。
The fungicidal compositions of this invention are generally most effective when added to aqueous systems having a pH above 7, preferably between 8 and 9. The individual germicidal components of the compositions of the invention can be added to the aqueous system separately or premixed and in amounts effective to inhibit microbial growth. 2-(decylthio)ethanamine is generally 0.7
1,2-
Dibromo-2,4-dicyanobutane is generally added in a concentration range of 4.0 to 12.0 ppm. The total concentration of disinfectant in the water system generally ranges from 5 to 14 ppm, and preferably from 5.2 to 13.2 ppm.

【0013】下記の実施例は本発明の原理に従って本発
明を説明するために示されるものであって、添付特許請
求の範囲に指示された以外の何等の方式においても本発
明を限定するものと解釈してはならない。特に断らない
限り総ての部及び百分率は重量を基準としている。
The following examples are presented to illustrate the invention in accordance with the principles of the invention and are not intended to limit the invention in any way other than as indicated in the appended claims. Must not be interpreted. All parts and percentages are by weight unless otherwise noted.

【0014】[0014]

【実施例】【Example】

【0015】[0015]

【実施例1】2−(デシルチオ)エタンアミン及び1,
2−ジブロモ−2,4−ジシアノブタンの配合物をエン
テロバクター・アエロゲネスATCC#13048に対
する相乗作用について評価した。結果は下記の通りであ
る。
[Example 1] 2-(decylthio)ethanamine and 1,
A formulation of 2-dibromo-2,4-dicyanobutane was evaluated for synergism against Enterobacter aerogenes ATCC #13048. The results are as follows.

【0016】[0016]

【表1】       2−(デシルチオ)          
1,2−ジブロモ−          相乗作用  
    エタンアミン               
 2,4−ジシアノブタン        指数   
     A1     A2      A    
    B1     B2      B  0.7
0  2.00  0.35    10.0  20
.0  0.50    0.85*  0.70  
2.00  0.35    20.0  20.0 
 1.00    1.35  0.70  2.00
  0.35    30.0  20.0  1.5
0    1.85  1.50  2.00  0.
35    60.0  20.0  3.00   
 3.35  1.50  2.00  0.75  
  10.0  20.0  0.50    1.2
5  1.50  2.00  0.75    20
.0  20.0  1.50    1.75  1
.50  2.00  0.75    30.0  
20.0  1.50    2.25  1.50 
 2.00  0.75    60.0  20.0
  3.00    3.75  2.00  2.0
0  1.00    10.0  20.0  0.
50    1.50  2.00  2.00  1
.00    20.0  20.0  1.00  
  2.00  2.00  2.00  1.00 
   30.0  20.0  1.50    2.
50  2.00  2.00  1.00    6
0.0  20.0  3.00    4.00  
4.00  2.00  2.00    10.0 
 20.0  0.50    2.50  4.00
  2.00  2.00    20.0  20.
0  1.00    3.00  4.00  2.
00  2.00    30.0  20.0  1
.50    3.50  4.00  2.00  
2.00    60.0  20.0  3.00 
   5.00
[Table 1] 2-(decylthio)
1,2-dibromo- synergy
Ethanamine
2,4-dicyanobutane index
A1 A2 A
B1 B2 B 0.7
0 2.00 0.35 10.0 20
.. 0 0.50 0.85* 0.70
2.00 0.35 20.0 20.0
1.00 1.35 0.70 2.00
0.35 30.0 20.0 1.5
0 1.85 1.50 2.00 0.
35 60.0 20.0 3.00
3.35 1.50 2.00 0.75
10.0 20.0 0.50 1.2
5 1.50 2.00 0.75 20
.. 0 20.0 1.50 1.75 1
.. 50 2.00 0.75 30.0
20.0 1.50 2.25 1.50
2.00 0.75 60.0 20.0
3.00 3.75 2.00 2.0
0 1.00 10.0 20.0 0.
50 1.50 2.00 2.00 1
.. 00 20.0 20.0 1.00
2.00 2.00 2.00 1.00
30.0 20.0 1.50 2.
50 2.00 2.00 1.00 6
0.0 20.0 3.00 4.00
4.00 2.00 2.00 10.0
20.0 0.50 2.50 4.00
2.00 2.00 20.0 20.
0 1.00 3.00 4.00 2.
00 2.00 30.0 20.0 1
.. 50 3.50 4.00 2.00
2.00 60.0 20.0 3.00
5.00

【0017】[0017]

【実施例2】[Example 2]

【0018】[0018]

【表2】      2−(デシルチオ)          1
,2−ジブロモ−          相乗作用   
  エタンアミン                2
,4−ジシアノブタン        指数     
   A1      A2    A       
  B1     B2      B  0.60 
 2.00  0.30      4.0  30.
0  0.13    IBR  0.60  2.0
0  0.30      8.0  30.0  0
.27    IBR  0.60  2.00  0
.30    12.0  30.0  0.40  
  IBR  0.80  2.00  0.40  
    4.0  30.0  0.13    IB
R  0.80  2.00  0.40      
8.0  30.0  0.27    0.67* 
 0.80  2.00  0.40    12.0
  30.0  0.40    0.80*  1.
20  2.00  0.60      4.0  
30.0  0.13    0.73*  1.20
  2.00  0.60      8.0  30
.0  0.13    0.87*  1.20  
2.00  0.60    12.0  30.0 
 0.13    1.00
[Table 2] 2-(decylthio) 1
,2-dibromo- synergy
Ethanamine 2
,4-dicyanobutane index
A1 A2 A
B1 B2 B 0.60
2.00 0.30 4.0 30.
0 0.13 IBR 0.60 2.0
0 0.30 8.0 30.0 0
.. 27 IBR 0.60 2.00 0
.. 30 12.0 30.0 0.40
IBR 0.80 2.00 0.40
4.0 30.0 0.13 IB
R 0.80 2.00 0.40
8.0 30.0 0.27 0.67*
0.80 2.00 0.40 12.0
30.0 0.40 0.80* 1.
20 2.00 0.60 4.0
30.0 0.13 0.73* 1.20
2.00 0.60 8.0 30
.. 0 0.13 0.87* 1.20
2.00 0.60 12.0 30.0
0.13 1.00

【0019】[0019]

【実施例の記号の説明】[Explanation of symbols in examples]

【0020】[0020]

【数1】相乗指数=A+B 上式中: A=A1/A2 B=B1/B2 上式中: A1=混合物における2−(デシルチオ)エタンアミン
の濃度(ppmA1) A2=2−(デシルチオ)エタンアミンのMIC終点B
1=混合物中における1,2−ジブロモ−2,4−ジシ
アノブタンの濃度(ppmA1) B2=1,2−ジブロモ−2,4−ジシアノブタンのM
IC終点 A+B=1の時:組み合わせ物は相加的である。
[Equation 1] Synergy index=A+B In the above formula: A=A1/A2 B=B1/B2 In the above formula: A1=Concentration of 2-(decylthio)ethanamine in the mixture (ppmA1) A2=Concentration of 2-(decylthio)ethanamine in the mixture (ppmA1) MIC end point B
1 = Concentration of 1,2-dibromo-2,4-dicyanobutane in the mixture (ppmA1) B2 = M of 1,2-dibromo-2,4-dicyanobutane
When IC endpoint A+B=1: the combination is additive.

【0021】A+B>1の時:組み合わせ物は拮抗的で
ある。
When A+B>1: the combination is antagonistic.

【0022】A+B<1の時:組み合わせ物は相乗的で
ある。
When A+B<1: the combination is synergistic.

【0023】注: *    =相乗作用 IBR  =細菌の減少は少ない MIC  =最低阻害濃度(Minimum Inhi
bitory Concentration)
Note: * = synergistic IBR = less bacterial reduction MIC = Minimum Inhibitory Concentration (Minimum Inhibitory Concentration)
bitory concentration)

Claims (7)

【特許請求の範囲】[Claims] 【請求項1】  微生物の成長を阻害するのに効果的な
量で2−(デシルチオ)エタンアミン及び1,2−ジブ
ロモ−2,4−ジシアノブタンの相乗作用的な混合物を
含んで成り、2−(デシルチオ)エタンアミン及び1,
2−ジブロモ−2,4−ジシアノブタンが夫々0.7−
1.2:4−12の重量比で存在する、微生物殺菌組成
物。
1. Comprising a synergistic mixture of 2-(decylthio)ethanamine and 1,2-dibromo-2,4-dicyanobutane in an amount effective to inhibit the growth of microorganisms, 2- (decylthio)ethanamine and 1,
2-dibromo-2,4-dicyanobutane is each 0.7-
A microbial killing composition present in a weight ratio of 1.2:4-12.
【請求項2】  微生物の成長を阻害するのに有効な量
で2−(デシルチオ)エタンアミン及び1,2−ジブロ
モ−2,4−ジシアノブタンの混合物を含んで成る組成
物を水系に添加することを特徴とする、水系中の微生物
の成長を阻害する方法。
2. Adding to an aqueous system a composition comprising a mixture of 2-(decylthio)ethanamine and 1,2-dibromo-2,4-dicyanobutane in an amount effective to inhibit the growth of microorganisms. A method for inhibiting the growth of microorganisms in an aqueous system, characterized by:
【請求項3】  水系が7より高いpHに保たれる、請
求項2に記載の方法。
3. The method of claim 2, wherein the aqueous system is maintained at a pH greater than 7.
【請求項4】  水系が8及び9の間のpHに保たれる
、請求項2に記載の方法。
4. A method according to claim 2, wherein the aqueous system is maintained at a pH between 8 and 9.
【請求項5】  2−(デシルチオ)エタンアミン及び
1,2−ジブロモ−2,4−ジシアノブタンが夫々0.
7−1.2:4−12の重量比で存在する、請求項2に
記載の方法。
5. 2-(decylthio)ethanamine and 1,2-dibromo-2,4-dicyanobutane each have a content of 0.
3. A method according to claim 2, wherein the weight ratio is 7-1.2:4-12.
【請求項6】  水系が冷却水系である、請求項2に記
載の方法。
6. The method of claim 2, wherein the water system is a cooling water system.
【請求項7】  水系が紙パルプ製造設備である、請求
項2に記載の方法。
7. The method of claim 2, wherein the aqueous system is a paper pulp production facility.
JP3307165A 1990-11-28 1991-10-28 Synergetically bactericidal composition of 2-(decylthio)ethaneamine and 1,2-dibromo- 2,4-dicyanobuthane Pending JPH04266802A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US07/618,859 US5124355A (en) 1990-11-28 1990-11-28 Synergistic microbiocidal composition of 2-(decylthio)ethaneamine and 1,2-dibromo-2,4-dicyanobutane
US618859 1990-11-28
SG153394A SG153394G (en) 1990-11-28 1994-10-21 Synergistic microbiocidal composition

Publications (1)

Publication Number Publication Date
JPH04266802A true JPH04266802A (en) 1992-09-22

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JP (1) JPH04266802A (en)
AU (1) AU641293B2 (en)
CA (1) CA2047583A1 (en)
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GB2250199B (en) 1994-05-04
AU8815891A (en) 1992-06-04
GB2250199A (en) 1992-06-03
US5124355A (en) 1992-06-23
CA2047583A1 (en) 1992-05-29
SG153394G (en) 1995-03-17
HK137494A (en) 1994-12-16
AU641293B2 (en) 1993-09-16

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